Process of alylation in the presence of water as catalyst



1949- a w. A. STOVER 2,460,719

PROCESS OF ALKYHATION IN THE PRESENCE OF WATER AS CATALYST Filed Dec. 1, 1945 40 60 80 PER (f/VT 14 197675 55.550 0N Wf/GHT UFHYDROCA/PBON CHARGE.

Patented Feb. 1, 1949 v PROCESS OF ALKYLATION IN THE PRES- ENCE OF WATER AS CATALYST William A. Stover, Woodbnry, N. 1.. mi imto Soconr-Vacuum Oil Company, Incorporated, a corporation of New York Application December 1, 1945, Serial No. 832,211

6 Claims. (Cl. 260-6834) This invention relates generally, to the alkylation of paraillnic hydrocarbons with oleilnic hydrocarbons, and is more particularly concerned with the production of high-octane motor fuels by the catalytic alkylation of paraflinic hydrocarbons with oleflnic hydrocarbons.

It is well known in the art to polymerize oleflnic hydrocarbon gases to produce motor fuels having constituents of an unsaturated character. Various commercial processes have been proposed for ultimately effecting the desired polymerization of the oleilnic hydrocarbons. These processes have been predicated upon the dictates of the chemical nature of the stocks available, as well as engineering considerations such as initial and operation costs; their essential feature being that in the course of treating the materials, the olefinic hydrocarbons produced in the earlier stages of the process, are eventually polymerized into hydrocarbons boiling withtin the gasoline boiling range. Accordingly, hydrocarbon gases may be passed along with cracking stock or naphtha through a cracking still to crack and polymerize such gases to gasoline simultaneously with the cracking or reforming, or paraflinic hydrocarbon gases may be separately cracked into oleflnic hydrocarbon gases and these gases are subsequently passed with naphtha through a polymerizing and reforming still. In some instances, the processes involve the use of catalysts for facilitating the cracking and/or polymerization operations.

It is also well known in the art to combine paraflinic hydrocarbons directly with olefinic hydrocarbons by processes broadly called alkylation processes, to produce motor fuels having constituents of saturated character. In alkylation processes, a charge comprising a mixture of an alkylatable paraflinic hydrocarbon, as a general rule, a parafllnic hydrocarbon other-than methane and ethane, called the parafllnic reactant, and an oleilnic hydrocarbon, called the olefinic reactant or alkylating agent, is subjected to high temperature and pressure to produce a saturated alkylate product. Since conditions of alkylation also cause polymerization of the oleflnic reactant,- it is necessary to maintain a relatively low concentration of the oleflnic reactant in the charge. The only'limit to the pressure used appears to be the feasibility of maintaining high pressures. On the other hand, the temperature used is limited by degradation of the hydrocarbon reactants in the charge to low molecular weight hydrocarbons, and the occurrence of side reactions, including polymerization of the olefinic reactant, under high temperature conditions, that substantially reduce the purity of the product obtained.

The temperatures and to a certain extent, the pressures employed in alkylation operations, de-

the absence or presence of alkylation catalysts. The two methods are generally referred to as thermal and catalytic alkylation, respectively. As is well known in the art, thermal alkylation ordinarily involves the use of temperatures of at least about 950 I". and pressures of the order of 4000 pounds per square inch or higher. At these temperatures, the degradation of the hydrocarbon reactants in the charge, and the occurrence of side reactions, including polymerization of the oleflnic reactant, is somewhat marked. On the other hand, catalytic alkylation involves the use or appreciably .lower temperatures, thereby assuring a high yield of desired alkylate by avoiding extensive degradation of the reactants, the occurrence of secondary reactions, and appreciable polymerization of the olefinic reactant.

Several methods are known for the catalytic alkylation of isoparafllnic hydrocarbons with oleflnic hydrocarbons. For instance, it is known to alkylate isoparafllnic hydrocarbons with oleflnic hydrocarbons in the presence of sulfuric acid, phosphoric acid, metal phosphates, metal halides, activated clays, and the like, as catalysts. In these catalytic alkylation processes, the hydrocarbon reactants form with the alkylation catalysts, a heterogeneous system during the alkylation operation. Hence, these alkylation catalysts may be termed heterogeneous alkylation catalysts. Since under alkylation conditions. the catalytic activity 0i' the alkylation catalysts appears to be predicated upon contact between the catalysts and the gaseous hydrocarbon reactants at the interfaces therebetween, in these processes, the catalysts are used in amounts varying between 10% and 20% by weight, on the charge, depending on the catalyst used. Due to these comparatively high amounts, where possible, recovery and regeneration of the catalysts have been proposed. This, of course, involves high initial and operation costs. Further, it is also known that certain substances called promoters, promote the catalytic activity of these alkylation catalysts. Accordingly, several processes have been proposed ing a normal parafllnic or isoparaiilnic hydrocar-.

bon and an oleflnic hydrocarbon in a reaction zone under alkylating conditions, with small or promoter amounts of what has been termed therein. a homogeneous gaseous phase alkylation pend upon whether the alkylation is eflected in catalyst. which consists essentially of a material that forms with the 3 hydrocarbon reactants. a single, homogeneous, gaseous phase under the alkylation conditions of the reactionv zone.

Another copending application, Serial Number 502,813, flied September 17, 1943 and now Patent No. 2,410,072, is directed to the process of alkylating isobutane with propylene, which, comprises contacting isobutane and propylene in a reaction one under closely controlled alkylating conditions, with promoter or small amounts of the homogeneous gaseous phase catalysts broadly disclosed in the copending application referred to hereinbefore. In the alkylation of isobutane with propylene in the presence of homogeneous gaseous phase alkylation catalysts, it was found that the alhlate obtained included constituents that are-entirely different from the constituents of the hydrocarbon alkylate obtained in the alkylation of isobutane with propylene in the presence of known heterogeneous alkylation catalysts, i. e., AlCla, H2804, and the like. Thus, when heterogeneous alkylation catalysts are used, 2,3-dimethylpentane and 2,4-dimethyl-pentane are important constituents of the hydrocarbon alkylate obtained. on the other hand, when homogeneous gaseous phase alkylation catalysts are employed, triptane or 2,2,3-trimethylbutane, 2,2-dimethylpentane, and Z-methylhexane are the predominant constituents of the hydrocarbon alkylate. In this copending application, the formation of these three compounds was postulated as follows:

From a motor fuel standpoint, the 2,2-dimethylpentane produced by the first reaction has an octane number of about 80 CFR motor method; the triptane produced by the second reaction has an octane number of well over 100; and the 2- methylhexane obtained in the third reaction has an octane number of about 45. In view of the foregoing, in the manufacture of high-octane motor fuels by the alkylation of isobutane with propylene, alkylation conditions that favor the production of triptane obviously are preferable. It was also found that in actual practice. it was impossible to obtain triptane exclusively, appreciable amounts of 2,2-dlmethylpentane and 2- methylhexane being always formed.-

-The specific classes of homogeneous gaseous phase catalysts disclosed in these copendlng applications are organic halogen compoimds, and, more particularly, chlorine and bromine. derivatives of acyclic hydrocarbons. chloroform, chlorinated naphtha, chlorinated butane. carbon bromide, dibromoisobutane, ethyl bromide, propylene tribromide, and tertiary monobromobutane are among the specific chlorine andbromine derivatives of acyclic hydrocarbons mentioned as suitable homogeneouagaseous phase alkylation catalyst for the allwlation processes disclosed in these copending applications.

The present invention is predicated on the use of water as a homogeneous gaseous phase alkylation catalyst, in the alkylation ofparamnic hydrocarbons with oleflnic hydrocarbons con-- taining at least three carbon atoms, under conditions of alkylation.

Accordingly, it is an object of the present invention to provide an efllcient process for alkylating alkyla/table isoparafllnic or alkylatable normal paramnic hydrocarbons with oleflnic hydrocarbons containing at least three carbon atoms. Another object is to provide an improved process for catalytically alkylating either alkylatable normal paraillnic hydrocarbons or alkylatable isoparaflinic hydrocarbons with oleflnic hydrocarbons containing at least three carbon atoms. A more specific object is to provide a process for catalytically alkylating alkylatable normally gaseous isoparaflinic hydrocarbons with normally gaseous oleflnic hydrocarbons containing at least three carbon atoms, to produce high yields of high-octane gasoline. A very important object is to aiford a. process for alkylating isobutane with propylene, to produce high yields of high-octane gasoline. A further object is to provide a process capable of carrying out the above objects by using water as a. homogeneous gaseous phase alkylation catalyst.

Other objects and advantages of the present invention will become apparent to those skilled in the artfrom the following description, taken in conlu'nction with the following drawing which shows a curve representing graphically the relationship between the yield per pass of the fraction of alkylate boiling at 70-86 C. (the fraction containing heptanes), based on the weight of oleflnic hydrocarbon charged, in the alkylation of isobutane with propylene, and the amount of water used as catalyst.

Broadly stated, my invention provides a process for alkylating alkylatable normal paraflinic or isoparamnic hydrocarbons, particularly isobutane, with oleflnic hydrocarbons containing at least three carbon atoms, particularly propylene, which comprises contacting. the paraflinic and oleflnic hydrocarbons in gaseous phase and in a reaction zone under alkylating conditions, with water.

An important feature is therelatively low temperature that may be used. As a result, degradation of the hydrocarbon reactants in the charge to low molecular weight hydrocarbons and the pronounced occurrence of side reactions, including polymerization of the oleflnic hydrocarbons, are substantially completely avoided. Consequently, in my process, I obtain high yields of a high grade. product that is almost entirely paraflinic in nature and is substantially free from impurities.

A very important feature of the present invention is the fact that, contrary to known catalytic alkylation processes of the prior art in which the hydrocarbon reactants being processed form with the alkylation cataylsts, a heterogeneous system during the alkylation operation, the alkylation process of my invention.

employs an alkylation catalyst consistingessentetrachloride, ethylene dibromide. propylene diti -11y f a material that forms with the hydrocarbon reactants being processed, a single,

is substantially eliminated and agitation and/or.

mixing problems are non-extant. Further, since the catalytic activity of alkylation catalysts appears to be predicated somewhat upon contact between the catalysts and the hydrocarbon reactants at the interfaces therebetween, it follows that the catalytic emciency of a given catalyst increases with the increase in area ofinterfacial contact, other variables remaining constant. Hence, since the homogeneous gaseous phase alkylation catalyst of my process inherently furnishes the greatest possble interfacial contact" between the catalyst and the hydrocarbon reactants under the conditions of alkylation, efficient catalytic activity with a concomitant high yield of high grade alkylate is possible although using relatively small amounts of homogeneous gaseous phase alkylation catalyst.

In view of the foregoing, an operation feature of the process of the present invention that is of considerable practical importance, is that relatively small amounts of water may be used as alkylation catalyst. These amounts are so small and water is so cheap that it may be discarded feasibly, thereby obviating recovery and regeneration problems and eliminating high initial and operation costs.

As indicated by the curve shown in the drawing, which is based on data obtained by alkylating isobutane with propylene in the presence of varying amounts of water, at a temperature of about 850 F. and a pressure of about 4500 pounds per square inch, when water is used in concentrations of up to about 30% based on the weight of the hydrocarbon charge, it has a beneficial effect upon the quality of alkylate, increasing the amounts of the 76-86 C. fraction of the alkylate containing the branched heptanes including triptane. Above about 30%, as indicated by the curve, water has an undesirable effect upon the quality of alkylate, decreasing the amounts of a the 76-86 C. fraction of the alkylate which would be obtained otherwise, Accordingly, in my process water is used in amounts of up to about 30% by weight, and preferably, in amounts varying between about 5% by weight and 25% by weight, with respect to total charge of hydrocarbonreactants. I

The paraflinic and olefinic hydrocarbons to be used in my process may be derived from any suitable source, as is well known in the art, and may be used either in the pure state or in admixture with other constituents not undesirable. The paraflinic and olefinic hydrocarbons usually employed in the preferred operation of manufacturing motor fuels, will be the normally gaseous parafilnic hydrocarbons, except methane and ethane, and the normally gaseous olefinic hydrocarbons, except ethylene, as is well understood in the art. I have found that when the oleflnic .reactant is ethylene, water does not catalyze the reaction, and that on the contrary, the yield of alkylate and specificity of the reaction are decreased by the presence of water.

A conventional and preferred source oi parafflnic and olefinic hydrocarbons suitable for the process of my invention is the fixed gases obtained around petroleum refineries. These fixed gases may furnish substantially all the desired paraffinic and olefinic hydrocarbons, or it may be necessary or desirable to obtain additional sill plies, as is well understood. Additional olefinic hydrocarbons, if required, may be formed from a portion of the parafilnic hydrocarbons. 0n the other hand. additional parafiinic hydrocarbons may be admixed to increase the concentration of parafiinic hydrocarbons to a desired magnitude.

In carrying out my process, I ordinarily use temperatures varying between about 700 1'', and about 850 F., and preferably, temperatures varying between about 775 F. and about 850 F} The alkylate produced under these conditions contains no more than 5% of olefinic hydrocarbons and no aromatics so that the predominance of alkylation obtained thereby is a distinct feature of the process. Under appreciably higher temperature conditions, secondary reactions occur that substantially reduce the purity of the product obtained.

The pressure to be used in my process may vary from about 500 pounds per square inch to about 6000 pounds per square inch or more, and preferably, from about 2500 pounds per square inch to about 6000 pounds per square inch, the most suitable pressure being more or less dependent upon the particular temperature involved. In general, the higher the pressure, the higher the yield of aikylate. Accordingly, the criterion for establishing an upper limit to the pressure range used is primarily the feasibility of maintaining such pressure.

The process may be carried out as a batch, con tinuous or semi-continuous type of operation. Particularly when the process is carried out on a commercial scale, economic considerations make it preferable to operate in a continuous manner. For efficient operation, whether the process is carried out on a batch or continuous basis, it is essential that the hydrocarbon reactants be inti-- mately contacted with the homogeneous gaseous phase catalysts of my invention. This may-be effected in several ways, as is well known in the art.

In my process it is desirable, as in known isoparafiln-olefin alkylation processes, to keep the concentration of the olefinic hydrocarbons relatively low during the alkylation reaction, in order to eliminate as much olefin polymerization as possible. Accordingly, it is advisable to maintain the olefin concentration in thelcharge below about 25% by volume, and preferably, between about 5% and about 12% by volume. In continuous operation, this is effected by introducing the olefinic reactant at a number of points in the reaction zone or by adding the olefinic reactant to a recirculating mass of excess paramnic hydrocarbon reactant, reaction product, and catalyst. I

- The reaction period during which the .reactants are present in the reaction zone, depends upon the temperature, and to a certain extent. upon the pressure. Ordinarily, a reaction period varying between 1- -2 minutes and 1-2 hours is satisfactory.

It must be understood, that the reaction variables are more or less interdependent, hence,-

when one is arbitrarily fixed, the limits within which the others may be varied, are somewhat before.

The alhlate product that I obtain distills over a fairly large boiling range, but a greater part of the alkylate, usually from about 85% to about 90%, distills in the'boiling range of aviation gasolines. The iodine number of the aviation distillate is low, on the order of about to 10. As mentioned hereinbefore, the alkylate product consists predominantly of branched parafilnic hydrocarbons.

. Numerous experimental data could be adduced to indicate the results obtainable by employing the homogeneous gaseous phase catalyst of the present invention, but the following examples are sufficiently characteristic:

Alleviation of isobutane with propylene to produce triptane continuous operation Bun No l 2 Temperature, F 850 850 Pressure, lbs. per sq. in 4, 500 4, 500 Contact Time, minutes l0. 2 15. 6 Water percent by weight oi Hydrocarbon Charge... 0 l0. 2 Propylene, percent by weight of Hydrocarbon Charge l0. 7 10. 8 Volume ercent oi Alkylate boiling between 76 an O 2i. 4 46. 8 Volume percent Triptane in 70-80? 0. Out of Alkylate. ll 6 hydrocarbon with an oleflnic hydrocarbon containing at least three carbon atoms, in gaseous phase and in a reaction zone under alkylating conditions including a temperature varying between about 700 F. and about 850 F. and a pressure of at least 500 pounds per square inch. in the presence of a catalyst comprising essentially water in amounts of up to about 30% by weight based on the hydrocarbon charge, and maintaining said alkylatable parafllnic hydrocarbon in excess over said oleiinic hydrocarbon in said reaction zone. so that alwlation is the principal reaction.

2. The process of manufacturing a high-octane motor fuel, which comprises contacting an alkylatable normallygaseous isoparaflinic hydrocarbon with a normally gaseous olefinic hydrocarbon containing at least three carbon atoms. in a gaseous phase and in a reaction zone under alkylating conditions including a temperature varying between about 700 1''. and about 850 F.

and a pressure of at least 500 pounds per square inch, in the presence of a catalyst comprising essentially water in amounts of up to about 30% by weight based on the hydrocarbon charge, and maintaining said alkylatable normally gaseous isoparafiinic hydrocarbon in excess over said normally gaseous oleflnic hydrocarbon in said reaction zone, so that alkylation is the principal reaction.

3. The process of manufacturing a high-octane motor fuel, which comprises contacting isobutane with propylene, in gaseous phase and in a reaction zone under alkylating conditions includ- 8 a temperature varying between about 700 1. and about 850 1''. and a pressure of at least 500 pounds per square inch, in the presence of a catalyst comprising essentially water in amounts of up to about 80% by weight based on the hydrocarbon charge, and maintaining said isobutane in excess over said propylene in said reaction zone.

. so that alblation is the principal reaction.

4. The process of alkylating alkylatable isobons containing at least three carbon atoms,

ing isobutane in excess over said propylene in which comprises contacting an almlatable isoparamnic hydrocarbon with an oleflnic hydrocarbon containing at least three carbon atoms. in gaseous phase and in a reaction zone under alblating conditions including a temperature varying between about 775 F. and about 850 F. and a pressure of"at least 2500 pounds per square inch, in the presence of a catalyst comprising essentially water in amounts varying between about 5% and about 25% by weight based on the hydrocarbon charge, and maintaining said alkylatable isoparaiiinic hydrocarbon in excess over said .oleflnic hydrocarbon in said reaction zone, so that alkylation is the principal reaction.

5. The process of manufacturing a high-octane motor fuel, which comprises contacting an alkylatable normally gaseous isoparaflinic hydrocarbon with a normally gaseous oleflnic hydrocarbon containing at least three carbon atoms in gaseous phase and in a reaction zone under alkylating conditions including a temperature varying between about 775 and about 850 F. and a pressure of at least 2500 pounds per square inch, in the presence of a catalyst comprising essentially water in amounts .varying between about 5% and about 25% by weight based on the hydrocarbon charge, and maintaining said alkylatable normally gaseous isoparafllnic hydrocarbon in excess over said normally gaseous oleiinic hydrocarbon in said reaction zone, so that alblation is the principal reaction.

6. The process of manufacturing triptane, which comprises contacting isobutane with propylene, in gaseous phase and in a reaction zone under alhlating conditions including a temperature varying between about 775 F. and about 850 F, and a pressure of at. least 2500 pounds per square inch. in the presence of a catalyst comprising essentially water in amounts varying between about 5% and about 25% by weight based on the hydrocarbon charge, and maintainsaid reaction zone, so that alkylation is the principal reaction.

. WIILIAM A. STOVER.

REFERENCES CITED The following references are of record in the I file of this patent: unrrnp s'rarns ra'rsu'rs.

Number Name Date 2,320,585 Vesterdal Aug. 10, 1943 2,328,586 vesterdal Aug. 10, 1943 2,326,587 Vesterdal' Aug. 10, 1943 2,370,751 Russell July 3, 1945 Certificate of Correction Patent No. 2,460,719. February 1, 1949. WILLIAM A. STOVER It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 20, for Withtin read within; column 2, line 37, for 20% read 200%; line 51, same column, for Patent 2,410,107 read Patent No. 2,410,107;

column 3, line 33, insert ISOBUTANE PROPYLENE; lines 41 and 42, for

our on, (IE read tin and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 21st day of June, A. D. 1949.

THOMAS F. MURPHY,

Assistant Uommzssimer of Patents. 

